CN105111729B - Environmental protection flame retardant carbon fiber reinforced polyamide composite material and its preparation method and application - Google Patents
Environmental protection flame retardant carbon fiber reinforced polyamide composite material and its preparation method and application Download PDFInfo
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- CN105111729B CN105111729B CN201510571583.8A CN201510571583A CN105111729B CN 105111729 B CN105111729 B CN 105111729B CN 201510571583 A CN201510571583 A CN 201510571583A CN 105111729 B CN105111729 B CN 105111729B
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- carbon fiber
- flame retardant
- environmental protection
- composite material
- fiber reinforced
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 84
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 76
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 76
- 239000004952 Polyamide Substances 0.000 title claims abstract description 66
- 229920002647 polyamide Polymers 0.000 title claims abstract description 66
- 239000011528 polyamide (building material) Substances 0.000 title claims abstract description 63
- 239000002131 composite material Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 65
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 39
- 239000002270 dispersing agent Substances 0.000 claims abstract description 14
- -1 nitrogen phosphorus Chemical compound 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims description 19
- 229920002292 Nylon 6 Polymers 0.000 claims description 16
- 238000005453 pelletization Methods 0.000 claims description 16
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 claims description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N al2o3 Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 230000003078 antioxidant Effects 0.000 claims description 6
- 239000003963 antioxidant agent Substances 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 5
- 230000000979 retarding Effects 0.000 claims description 5
- 230000002195 synergetic Effects 0.000 claims description 5
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- 229920000297 Rayon Polymers 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol Chemical class OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N Cyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 2
- 150000007973 Cyanuric acids Chemical class 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L Iron(II) chloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- 229910001884 aluminium oxide Inorganic materials 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 239000011304 carbon pitch Substances 0.000 claims description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N cyanoguanidine Chemical class NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000412 dendrimer Substances 0.000 claims description 2
- 229920000736 dendritic polymer Polymers 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- 238000011017 operating method Methods 0.000 claims description 2
- 150000008301 phosphite esters Chemical group 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims 1
- 230000005494 condensation Effects 0.000 claims 1
- 238000001125 extrusion Methods 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 4
- 239000002861 polymer material Substances 0.000 abstract description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 22
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 14
- 238000001816 cooling Methods 0.000 description 13
- 239000002033 PVDF binder Substances 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 238000003892 spreading Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 150000003008 phosphonic acid esters Chemical class 0.000 description 10
- 239000000835 fiber Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical group 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- ULINDIVVCBSIPZ-UHFFFAOYSA-N (2,4-ditert-butylphenyl) phosphite Chemical class CC(C)(C)C1=CC=C(OP([O-])[O-])C(C(C)(C)C)=C1 ULINDIVVCBSIPZ-UHFFFAOYSA-N 0.000 description 2
- WSEFPKKOUNRCAJ-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;octadecanoic acid Chemical compound OCC(CO)(CO)CO.CCCCCCCCCCCCCCCCCC(O)=O WSEFPKKOUNRCAJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006011 modification reaction Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- ARWLNYJOVMFZNY-KVVVOXFISA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;(Z)-octadec-9-enoic acid Chemical group OCC(CO)(CO)CO.CCCCCCCC\C=C/CCCCCCCC(O)=O ARWLNYJOVMFZNY-KVVVOXFISA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 101710014322 MDV028 Proteins 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- RSJKGSCJYJTIGS-UHFFFAOYSA-N Undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical class [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 125000006367 bivalent amino carbonyl group Chemical group [H]N([*:1])C([*:2])=O 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000005712 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing Effects 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 229920005570 flexible polymer Polymers 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003014 reinforcing Effects 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
Abstract
The invention belongs to modified polymer material field, discloses a kind of environmental protection flame retardant carbon fiber reinforced polyamide composite material and its preparation method and application.The composite material includes the component of following mass fraction：Polyamide 7.7~70.7%；Carbon fiber 15~55%；Kynoar 10~25%；Composite flame-retardant agent 4~15%；Dispersant 0.2~1%；Other auxiliary agents 0.1~0.3%.The Kynoar of high molecular weight and the excellent compatibility of polyamide material can form big network structure in polymeric substrate, make composite material that there is certain flame retardant property, the nitrogen phosphorus flame retardant of appropriate amount is added, which can reach higher environmental protection flame retardant grade.The present invention greatly reduces the dosage of fire retardant, carbon fiber reinforced polyamide material is reduced density of material while best mechanical property is reached, improve the fire resistance of material by adding Kynoar.
Description
Technical field
The invention belongs to modified polymer material field, more particularly to a kind of environmental protection flame retardant carbon fiber reinforced polyamide is compound
Material and its preparation method and application.
Background technology
Polyamide be on molecular backbone containing recurring amide radical group-[NHCO]-thermoplastic resin general name.This kind of polymer
With many excellent performances such as wear-resisting, oil resistant, self-lubricating, impact resistance, and it is widely used in mechanical equipment, automobile making, instrument
The fields such as instruments and meters.Highly polar amide group and long flexible aliphatic segment in fatty polyamide molecular structure make this kind of
Material has limited oxygen index low, meets the shortcomings of fire easily burns.The especially polyamide of some glasses or fibre reinforced
For material when doing thin-gage goods, due to glass fibre or the wick effect of carbon fiber, it is fire-retardant that this kind of material is difficult to realize material
With the balance of toughness.Therefore, the temperature in use and environmental protection flame retardant performance of polyamide material how are improved, is that polyamide material is modified
The important research topic in one, field.
Carbon fiber is a kind of new fiber materials of phosphorus content more than 95%, it is with organic fiber, such as acrylics filament
(PAN), pitch and viscose rayon etc. do raw material, the micro crystal graphite fiber obtained in inert gas after high-temperature calcination graphite
Material.Since carbon fiber has in physical property, proportion is small, intensity is big, modulus is high, linear expansion coefficient is small, electric conductivity is strong, leads
The features such as heating rate is high, this kind of material are had been widely used in the enhancing and functional modification of thermoplasticity and thermosetting resin.Profit
Its physical and mechanical property of the thermoplastic being modified with carbon fiber and heat resistance have great raising, such as polyamide 66 material
The tensile strength of material improves nearly 3 times after the carbon fiber of material addition 20%, and bending modulus improves nearly 4 times, and heat distortion temperature carries
Up to 250 DEG C.By the optimization to surface treatment of carbon fibers mode and complex machining process, carbon fiber modifying polyamide material is improved
The performance of material, will be an important research direction of following reinforced polyamide development.
The characteristics of higher and higher, the present invention are required to the lightening and high performance of material for Current electronic electric field
A kind of environmental protection flame retardant carbon fiber reinforced polyamide composite material is developed, which is suitable for preparing by injection molding light
Quantify more demanding thin-gage goods, applied to requiring environmental protection flame retardant, antistatic and more demanding to material mechanical performance electricity
Sub- device and electric tool.
The content of the invention
In order to overcome the shortcomings and deficiencies of the prior art described above, primary and foremost purpose of the invention is to provide a kind of environmental protection flame retardant
Carbon fiber reinforced polyamide composite material.The composite material of the present invention has high intensity, high fire-retardance grade, low-density, low warpage
The features such as rate.
Another object of the present invention is to provide a kind of preparation of above-mentioned environmental protection flame retardant carbon fiber reinforced polyamide composite material
Method.
Still a further object of the present invention be to provide above-mentioned environmental protection flame retardant carbon fiber reinforced polyamide composite material electronic apparatus,
The application in the fields such as high iron, electric tool.Thin-gage goods prepared by the composite material of the present invention has intensity height, anti-flammability
Can be good, warpage is low the features such as, need to use thin-walled material particularly suitable for preparing laptop, phone housing, capacitor etc.
The field of material.
The purpose of the present invention is realized by following proposal：
A kind of carbon fiber reinforced polyamide composite material of environmental protection flame retardant, includes the component of following mass fraction：
The mass fraction of above-mentioned polyamide is preferably 40~50%.
Above-mentioned polyamide can be at least one of polyamide 6 (PA6) and polyamide 66 (PA66), be preferably polyamide
6。
It is furthermore preferred that the low-viscosity polyamides 6 that it is 2.0~2.8Pas that above-mentioned polyamide, which is viscosity,.
The mass fraction of above-mentioned carbon fiber is preferably 30~40%.
Above-mentioned carbon fiber can be in the carbon fiber of polyacrylonitrile base material, viscose carbon fiber and pitch silk carbon fiber extremely
Few one kind.
Preferably, above-mentioned carbon fiber is the carbon fiber of polyacrylonitrile base material.
It is furthermore preferred that above-mentioned carbon fiber is 4~8 μm of filament diameter, the polyacrylonitrile of 200~800tex of synnema line density
The carbon fiber of base material.The carbon fiber strength is high, can effectively improve the shock resistance of polyamide.
The mass fraction of above-mentioned Kynoar is preferably 12~20%.
Above-mentioned Kynoar (PVDF) is preferably the high molecular weight PVDF that molecular weight is more than or equal to 1,000,000, is such as included：
5301,9009 etc. of U.S. Su Wei, wherein more preferably 5301., can since Kynoar has higher limited oxygen index
To improve the flame retardancy of composite material；In addition the Kynoar of high molecular weight can form net structure in the composite,
It can prevent material from producing drip phenomenon in combustion.In addition, high molecular weight Kynoar can also be used as toughener effective
Improve the shock resistance of material.
Above-mentioned composite flame-retardant agent is formed by halogen-free flame retardants and synergistic flame retardant compounding.
Above-mentioned halogen-free flame retardants is the expansion type flame retardant of triazines.
Preferably, above-mentioned halogen-free flame retardants can be cyanurate, cyanurate derivative, melamine polyphosphate, guanidinesalt
At least one of with dicyandiamide salt.
It is furthermore preferred that above-mentioned halogen-free flame retardants is melamine polyphosphate.
Above-mentioned fire retarding synergist is the inorganic salts compound of reaction of decomposing that can be heated in alkaline conditions.
Preferably, above-mentioned fire retarding synergist is iron chloride (FeCl3), zinc borate (2ZnO3B2O3·3.5H2O), oxygen
Change magnesium (MgO) and aluminium oxide (Al2O3At least one of).
It is furthermore preferred that above-mentioned fire retarding synergist is FeCl3。
The mass ratio of halogen-free flame retardants and synergistic flame retardant is 5 in above-mentioned composite flame-retardant agent:1~2:1, it is preferably 3:1.
The mass fraction of above-mentioned dispersant is preferably 0.5~0.8%.
Above-mentioned dispersant can be pentaerythritol esters dispersant, silicone dispersant and dendrimer at least
It is a kind of.
Preferably, above-mentioned dispersant is pentaerythritol oleate, pentaerythritol stearate (PETS), the double hard esters of ethylene
At least one of acid amides (EBS) and organic silicon dispersant (such as E525, Evonik).
It is furthermore preferred that above-mentioned dispersant is organic silicon dispersant (such as E525, Evonik).
The mass fraction of above-mentioned other auxiliary agents is preferably 0.2%.
Above-mentioned other auxiliary agents can be this area it is common suitable at least one of processing aid of polyamide system,
Such as processing stabilizers, antioxidant.
Preferably, above-mentioned antioxidant for phosphite ester kind antioxidant (such as 3,9- bis- (2,4- dicumyl phenoxy group) -2,4,
8,10- tetra- oxa- -3,9- bis- phospha spiral shell [5.5] hendecane (S9228), three (2,4- di-tert-butyl-phenyl) phosphite esters
(168))。
It is furthermore preferred that above-mentioned antioxidant is three (2,4- di-tert-butyl-phenyl) phosphite esters (irgasfos 168).
Present invention also offers a kind of preparation method of above-mentioned environmental protection flame retardant carbon fiber reinforced polyamide composite material, including
Operating procedure in detail below：
(1) polyamide, Kynoar, composite flame-retardant agent, dispersant and other auxiliary agents are added in homogenizer and mixed
Close uniform；
(2) mixed material in step (1) is added in double screw extruder by main spout, carbon fiber is through twin-screw
Extruder vent is added in double screw extruder, and melt blending, extruding pelletization, that is, obtain environmental protection flame retardant fibre reinforced polyamides
Amine composite material.
It is room temperature~80 DEG C that the optimum condition of mixing described in step (1), which refers to mixing temperature, 200~400r/min's
10~30min is stirred under speed.
The screw speed of the host of double screw extruder described in step (2) is 350~430r/min, hopper feed spiral shell
The rotating speed of bar is 24~35r/min.
The temperature of melt blending described in step (2) is preferably that the temperature of each bringing-up section of extruder is 180~255 DEG C.
Extruding pelletization described in step (2) is preferably through extruding pelletization again after water-bath cooling system.
The physical and mechanical property for the environmental protection flame retardant carbon fiber reinforced polyamide composite material that the present invention is prepared, processability
Energy, appearance are functional, and relatively common carbon fiber reinforced polyamide material has the resistance to warping of higher, can be applied to electricity
In the fields such as sub- electric appliance, high iron, electric tool.Be particularly suitable for application prepare some will to the strength of materials and lightweight
Seek high thin-gage goods.
Kynoar is a kind of flexible polymer of high Oil repellent, and compared to polytetrafluoroethylene (PTFE), its crystallinity is lower, with
The compatibility of polyamide material is more preferable.The present invention is compound using Kynoar and polyamide, as polymerization after molten alloy
Thing base material, makes composite material have certain flame retardant property, and the material can reach after the nitrogen phosphorus flame retardant of appropriate amount is added
To higher environmental protection flame retardant grade.Kynoar with it is polyamide blended after can accelerate the crystallization rate of polyamide substrate, make
Obtained carbon fiber reinforced polyamide material has excellent physical and mechanical property, and has lower molding shrinkage and warpage
Rate.
The fire retardant mechanism of composite material of the present invention is：The good phase of the Kynoar of high molecular weight and polyamide material
Capacitive can form big network structure in polymeric substrate, on the one hand which can improve the limit of base material
Oxygen index (OI), on the other hand can play the role of anti-dripping melt during material combustion；Nitrogen phosphorus flame retardant can be fired in base material
The high-temperature material surface of burning forms the carbon-coating of densification, and discharges non-flammable gases and form protective layer to base material；Carbon fiber conduct
Reinforcing material can both provide the mechanical property of higher for composite material, and high carbon skeleton can be also used as in the combustion process of material
More preferable protection is formed in the burning surface of material；On the one hand synergistic flame retardant used in the present invention can be used as catalyst to promote
Reacted into nitrogen phosphorus flame retardant into carbon, still further aspect can occur under the high temperature and alkaline condition that polyamide substrate is burnt
Decomposition reaction, absorbs the heat produced in combustion process.
The present invention is had the following advantages and beneficial effect relative to the prior art：
(1) environmental protection flame retardant carbon fiber reinforced polyamide composite material of the invention has good mechanical property, relatively low
Molding shrinkage and warpage, are very helpful for the warpage properties tool for reducing material.
(2) present invention greatly reduces the dosage of fire retardant, makes fibre reinforced polyamides by adding Kynoar
Amine material reduces density of material while best mechanical property is reached, and improves the fire resistance of material.
Embodiment
With reference to embodiment, the present invention is described in further detail, but the implementation of the present invention is not limited to this.
Agents useful for same is commercially available in the following example.
Double screw extruder used is that draw ratio L/D is 40 in the following example:1, screw diameter is the parallel of 30mm
Double screw extruder, the screw speed of host is 350r/min, and the rotating speed of hopper feed screw rod is 28r/min, sets extruder
Each section of temperature from hopper to die head is respectively (totally nine area)：180 DEG C, 225 DEG C, 230 DEG C, 240 DEG C, 245 DEG C, 255 DEG C, 250
DEG C, 245 DEG C, 245 DEG C.
Embodiment 1
By the PA6 (M2400, Yueyang petrochemical industry) of 826g, the PVDF (5301, SOLEF) of 240g, the composite flame-retardant agent of 220g
(melamine polyphosphate and FeCl3Mass ratio be 3:1), the organosilicone spreading agent (E525, Evonik) of 10g, the Asia of 4g
Phosphonic acid ester irgasfos 168 is added in high speed blender, after stirring 10min at a temperature of 50 DEG C with the speed of 150r/min,
Said mixture material is added in double screw extruder by main spout, at the same by the carbon fiber of 700g (T700SC-12K,
Toray) it is added to by exhaust outlet in double screw extruder, environmental protection flame retardant carbon fiber is obtained after melt blending, water cooling pelletizing, drying
Reinforced polyamide composite material.
Embodiment 2
By the PA6 (M2400, Yueyang petrochemical industry) of 666g, the PVDF (5301, SOLEF) of 400g, the composite flame-retardant agent of 220g
(melamine polyphosphate and FeCl3Mass ratio be 3:1), the organosilicone spreading agent (E525, Evonik) of 10g, the Asia of 4g
Phosphonic acid ester irgasfos 168 is added in high speed blender, after stirring 10min at a temperature of 50 DEG C with the speed of 150r/min,
Said mixture material is added in double screw extruder by main spout, at the same by the carbon fiber of 700g (T700SC-12K,
Toray) it is added to by exhaust outlet in double screw extruder, environmental protection flame retardant carbon fiber is obtained after melt blending, water cooling pelletizing, drying
Reinforced polyamide composite material.
Embodiment 3
By the PA6 (M2400, Yueyang petrochemical industry) of 766g, the PVDF (5301, SOLEF) of 300g, the composite flame-retardant agent of 220g
(melamine polyphosphate and FeCl3Mass ratio be 3:1), the organosilicone spreading agent (E525, Evonik) of 10g, the Asia of 4g
Phosphonic acid ester irgasfos 168 is added in high speed blender, after stirring 10min at a temperature of 50 DEG C with the speed of 150r/min,
Said mixture material is added in double screw extruder by main spout, at the same by the carbon fiber of 700g (T700SC-12K,
Toray) it is added to by exhaust outlet in double screw extruder, environmental protection flame retardant carbon fiber is obtained after melt blending, water cooling pelletizing, drying
Reinforced polyamide composite material.
Embodiment 4
By the PA6 (M2400, Yueyang petrochemical industry) of 1106g, the PVDF (5301, SOLEF) of 300g, the composite flame-retardant agent of 80g
(melamine polyphosphate and FeCl3Mass ratio be 3:1), the organosilicone spreading agent (E525, Evonik) of 10g, the Asia of 4g
Phosphonic acid ester irgasfos 168 is added in high speed blender, after stirring 10min at a temperature of 50 DEG C with the speed of 150r/min,
Said mixture material is added in double screw extruder by main spout, at the same by the carbon fiber of 700g (T700SC-12K,
Toray) it is added to by exhaust outlet in double screw extruder, environmental protection flame retardant carbon fiber is obtained after melt blending, water cooling pelletizing, drying
Reinforced polyamide composite material.
Embodiment 5
By the PA6 (M2400, Yueyang petrochemical industry) of 760g, the PVDF (5301, SOLEF) of 300g, the composite flame-retardant agent of 220g
(melamine polyphosphate and FeCl3Mass ratio be 3:1), the organosilicone spreading agent (E525, Evonik) of 16g, the Asia of 4g
Phosphonic acid ester irgasfos 168 is added in high speed blender, after stirring 10min at a temperature of 50 DEG C with the speed of 150r/min,
Said mixture material is added in double screw extruder by main spout, at the same by the carbon fiber of 700g (T700SC-12K,
Toray) it is added to by exhaust outlet in double screw extruder, environmental protection flame retardant carbon fiber is obtained after melt blending, water cooling pelletizing, drying
Reinforced polyamide composite material.
Embodiment 6
By the PA6 (M2400, Yueyang petrochemical industry) of 866g, the PVDF (5301, SOLEF) of 300g, the composite flame-retardant agent of 220g
(melamine polyphosphate and FeCl3Mass ratio be 3:1), the organosilicone spreading agent (E525, Evonik) of 10g, the Asia of 4g
Phosphonic acid ester irgasfos 168 is added in high speed blender, after stirring 10min at a temperature of 50 DEG C with the speed of 150r/min,
Said mixture material is added in double screw extruder by main spout, at the same by the carbon fiber of 600g (T700SC-12K,
Toray) it is added to together in double screw extruder by exhaust outlet, environmental protection flame retardant carbon is obtained after melt blending, water cooling pelletizing, drying
Fibre-reinforced polyamide composite material.
Embodiment 7
By the PA6 (M2400, Yueyang petrochemical industry) of 666g, the PVDF (5301, SOLEF) of 300g, the composite flame-retardant agent of 220g
(melamine polyphosphate and FeCl3Mass ratio be 3:1), the organosilicone spreading agent (E525, Evonik) of 10g, the Asia of 4g
Phosphonic acid ester irgasfos 168 is added in high speed blender, after stirring 10min at a temperature of 50 DEG C with the speed of 150r/min,
Said mixture material is added in double screw extruder by main spout, at the same by the carbon fiber of 800g (T700SC-12K,
Toray) it is added to by exhaust outlet in double screw extruder, environmental protection flame retardant carbon fiber is obtained after melt blending, water cooling pelletizing, drying
Reinforced polyamide composite material.
Embodiment 8
By the PA6 (M2400, Yueyang petrochemical industry) of 366g, the PVDF (5301, SOLEF) of 300g, the composite flame-retardant agent of 220g
(melamine polyphosphate and FeCl3Mass ratio be 3:1), the organosilicone spreading agent (E525, Evonik) of 10g, the Asia of 4g
Phosphonic acid ester irgasfos 168 is added in high speed blender, after stirring 10min at a temperature of 50 DEG C with the speed of 150r/min,
Said mixture material is added in double screw extruder by main spout, at the same by the carbon fiber of 1100g (T700SC-12K,
Toray) it is added to by exhaust outlet in double screw extruder, environmental protection flame retardant carbon fiber is obtained after melt blending, water cooling pelletizing, drying
Reinforced polyamide composite material.
Embodiment 9
By the PA6 (M2400, Yueyang petrochemical industry) of 800g, the PVDF (5301, SOLEF) of 300g, the composite flame-retardant agent of 220g
(melamine polyphosphate and FeCl3Mass ratio be 3:1), the organosilicone spreading agent (E525, Evonik) of 10g, the Asia of 4g
Phosphonic acid ester irgasfos 168 is added in high speed blender, after stirring 10min at a temperature of 50 DEG C with the speed of 150r/min,
Said mixture material is added in double screw extruder by main spout, at the same by the carbon fiber of 666g (T700SC-12K,
Toray) it is added to by exhaust outlet in double screw extruder, environmental protection flame retardant carbon fiber is obtained after melt blending, water cooling pelletizing, drying
Reinforced polyamide composite material.
Embodiment 10
By the PA6 (M2400, Yueyang petrochemical industry) of 1000g, the PVDF (5301, SOLEF) of 300g, the composite flame-retardant agent of 220g
(melamine polyphosphate and FeCl3Mass ratio be 3:1), the organosilicone spreading agent (E525, Evonik) of 10g, the Asia of 4g
Phosphonic acid ester irgasfos 168 is added in high speed blender, after stirring 10min at a temperature of 50 DEG C with the speed of 150r/min,
Said mixture material is added in double screw extruder by main spout, at the same by the carbon fiber of 466g (T700SC-12K,
Toray) it is added to by exhaust outlet in double screw extruder, environmental protection flame retardant carbon fiber is obtained after melt blending, water cooling pelletizing, drying
Reinforced polyamide composite material.
Comparative example 1
By the PA6 (M2400, Yueyang petrochemical industry) of 1066g, composite flame-retardant agent (melamine phosphate and the FeCl of 220g3's
Mass ratio is 3:1), the organosilicone spreading agent (E525, Evonik) of 10g, the phosphiinic acid ester irgasfos 168 of 4g are added at a high speed
In blender, after stirring 10min at a temperature of 50 DEG C with the speed of 150r/min, said mixture material is added by main spout
Enter in double screw extruder, while the carbon fiber (T700SC-12K, Toray) of 700g is added to twin-screw by exhaust outlet and is squeezed
Go out in machine, carbon fiber reinforced polyamide composite material is obtained after melt blending, water cooling pelletizing, drying.
Comparative example 2
By the PA6 (M2400, Yueyang petrochemical industry) of 886g, composite flame-retardant agent (melamine polyphosphate and the FeCl of 400g3
Mass ratio be 3:1), the organosilicone spreading agent (E525, Evonik) of 10g, the phosphiinic acid ester irgasfos 168 of 4g are added to height
In fast blender, after stirring 10min at a temperature of 50 DEG C with the speed of 150r/min, said mixture material is passed through into main spout
Add in double screw extruder, while the carbon fiber (T700SC-12K, Toray) of 700g is added to twin-screw by exhaust outlet
In extruder, carbon fiber reinforced polyamide composite material is obtained after melt blending, water cooling pelletizing, drying.
The carbon fiber reinforced polyamide material that embodiment 1~10 and comparative example 1~2 are prepared is according to GB, ISO
Mechanical property and fire resistance test are carried out with standards such as UL94, the results are shown in Table 1.
The performance test of 1 carbon fiber reinforced polyamide composite material of table
By embodiment 1~10 as it can be seen that the environmental protection flame retardant carbon fiber reinforced polyamide material of the present invention has excellent physics
Mechanical property and good processing performance.Since Kynoar has higher limited oxygen index, using Kynoar with
The carbon fibre reinforced composite obtained after polyamide is compound can largely reduce the dosage of fire retardant, and flame retarding efficiency can reach
To the flame retardant rating of UL94-1.6mm V0, and the material flame retardant effect for not adding Kynoar is poor, even if substantial increase resistance
The dosage flame retardant effect of combustion agent is only capable of the level (comparative example 2) for reaching UL94-1.6mm V1, and burning time is compared with embodiment
It is long.Result of the test again shows that, when not having to add Kynoar in system, the impact strength of material and elongation at break be all
Having largely reduces, this explanation Kynoar can play good toughening effect in the composite.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention and from above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (8)
1. a kind of environmental protection flame retardant carbon fiber reinforced polyamide composite material, it is characterised in that by the component group of following mass fraction
Into：
The Kynoar is more than or equal to 1,000,000 high molecular weight Kynoar for molecular weight；
The carbon fiber is at least one in the carbon fiber, viscose carbon fiber and pitch silk carbon fiber of polyacrylonitrile base material
Kind；
The composite flame-retardant agent is made of halogen-free flame retardants and synergistic flame retardant；
The halogen-free flame retardants is in cyanurate, cyanurate derivative, melamine polyphosphate, guanidinesalt and dicyandiamide salt
It is at least one；
The fire retarding synergist is at least one of iron chloride, zinc borate, magnesia and aluminium oxide.
2. environmental protection flame retardant carbon fiber reinforced polyamide composite material according to claim 1, it is characterised in that：Described is poly-
The mass fraction of acid amides is 40~50%；The mass fraction of the carbon fiber is 30~40%；The Kynoar
Mass fraction is 12~20%.
3. environmental protection flame retardant carbon fiber reinforced polyamide composite material according to claim 1, it is characterised in that：
The polyamide is at least one of polyamide 6 and polyamide 66；
The dispersant is at least one of pentaerythritol esters dispersant, silicone dispersant and dendrimer；
Other described auxiliary agents are at least one of processing stabilizers and antioxidant.
4. environmental protection flame retardant carbon fiber reinforced polyamide composite material according to claim 1, it is characterised in that：Described answers
It is 5 to close the mass ratio of halogen-free flame retardants and synergistic flame retardant in fire retardant:1~2:1.
5. environmental protection flame retardant carbon fiber reinforced polyamide composite material according to claim 3, it is characterised in that：Described is anti-
Oxygen agent is phosphite ester kind antioxidant.
A kind of 6. preparation according to Claims 1 to 5 any one of them environmental protection flame retardant carbon fiber reinforced polyamide composite material
Method, it is characterised in that including operating procedure in detail below：
(1) polyamide, Kynoar, composite flame-retardant agent, dispersant and other auxiliary agents are added in homogenizer and mixed
It is even；
(2) mixed material in step (1) is added in double screw extruder by main spout, carbon fiber is through twin-screw extrusion
Machine exhaust outlet is added in double screw extruder, and melt blending, extruding pelletization, that is, obtain environmental protection flame retardant carbon fiber reinforced polyamide and answer
Condensation material.
7. the preparation method of environmental protection flame retardant carbon fiber reinforced polyamide composite material according to claim 6, its feature exist
In：
The condition mixed described in step (1) is that mixing temperature is room temperature~80 DEG C, is stirred under the speed of 200~400r/min
10~30min；
The screw speed of the host of double screw extruder described in step (2) is 350~430r/min, hopper feed screw rod
Rotating speed is 24~35r/min；
The temperature of melt blending described in step (2) is that the temperature of each bringing-up section of extruder is 180~255 DEG C.
8. according to Claims 1 to 5 any one of them environmental protection flame retardant carbon fiber reinforced polyamide composite material electronic apparatus,
Application in high iron and field of power tools.
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Denomination of invention: Environment-friendly flame-retardant carbon fiber reinforced polyamide composite and preparation method and application thereof Effective date of registration: 20190530 Granted publication date: 20180417 Pledgee: Conghua Branch of Guangzhou Bank Co., Ltd. Pledgor: GUANGZHOU SUPER-DRAGON ENGINEERING PLASTICS CO., LTD. Registration number: 2019440000196 |
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Date of cancellation: 20200821 Granted publication date: 20180417 Pledgee: Conghua Branch of Guangzhou Bank Co.,Ltd. Pledgor: GUANGZHOU SUPER-DRAGON ENGINEERING PLASTICS Co.,Ltd. Registration number: 2019440000196 |